Azo compounds and material colored therewith



Patented July 22, 1941 AZO COMPOUNDS AND MATERIAL COLORED THEREWITHJoseph B.

Dickey and James G. McNally, Rochester, N. Y., assignors to EastmanKodak Company, Rochester, N. Y.,

Jersey a corporation of New No Drawing. Application November 14, 1939,

Serial No. 304,364

15 Claims. (Cl. 260-152) This invention relates to azo compounds andtheir application to the art of dyeing or coloring.

We have discovered that the azo compounds having the general formula:

group, wherein R2 represents a member selected from the group consistingof an alkyl group, a cycloalkyl group, an allyl group, a phenyl nucleusand a furyl group, attached to its aliphatic portion, wherein saidtetrahydroquinollne and phenmorpholine nuclei contain an aliphatic groupjoined through a carbon atom of the aliphatic group to their nuclearnitrogen atom and wherein said aliphatic group contains a I group,wherein R2 has the meaning given above, attached thereto, constitute avaluable class of compounds. Depending upon their structure the azocompounds of our invention possess application for the dyeing orcoloration of organic derivatives of cellulose, silk and wool.

Both sulfonated and non'sulfonated compounds are included within thescope of our invention.

.pounds havebeen found to be especially of value for the dyeing oforganic derivatives of cellulose The nuclear non-sulfonatedj comand itis to these compounds and their application for the dyeing of organicderivatives of'cellulose that our invention is particularly directed.These nuclear non-sulionated compounds likewise possess some applicationfor the dyeing of wool and silk. For the dyeing of organic derivativesof cellulose such as cellulose acetate,

silk, nuclear non-sulfonated dye compounds wherein A is an aryl nucleusof the benzene series and R is a phenyl nucleus are generallyadvantageous.

The nuclear sulfonated compounds of our invention have little or noutility for the dyeing of organic derivatives of cellulose but possessapplication for the dyeing of silk and wool. Preferably when the dyecompounds of our invention are to be employed for the dyeing of organicderivatives of cellulose, they should contain no nuclear free carboxylicacid group. Red, yellow, orange-yellow, orange-red, blue-green, blue andviolet dyeings, for example, can be obtained employing the dye compoundsof our invention.

It is an object ofour invention to provide a new class of azo dyessuitable for the dyeing or coloration of textile materials made of orcontaining an organic derivative of cellulose, wool and silk. Anotherobject of our invention is to provide a process for the dyeing orcoloration of organic derivatives of cellulose, wool and silk. A furtherobject is to produce dyed textile materials which are of good fastnessto light and washing. A particular object of our invention is to providea new class of nuclear non-sulfonated azo dyes suitable for the dyeingor coloration of cellulose acetate silk. Other objects will hereinafterappear.

Typical organic derivatives of cellulose include the hydrolyzed as wellas the unhydrolyzed cellulose organic acid esters such ascelluloseacetate, cellulose formate, cellulose propionate or cellulose butyrateand the hydrolyzed as well as the unhydrolyzed mixed organic acid estersof cellulose such as cellulose acetate-propionate, celluloseacetate-butyrate, and the cellulose ethers such as methyl cellulose,ethyl cellulose or benzyl cellulose. While our invention will beillustrated .more particularly in connection with the coloration ofcellulose acetate silk, a material to which the invention is especiallyadapted, it will be understood that it applies to the coloration ofother organic derivatives of cellulose such as those just named as wellas to the coloration of wool and silk.

The azo compounds of our invention can be prepared by diazotizing adiazotizable member selected from the.group consisting of an arylamineof the benzene series and an aminobenzo thiazole and coupling thediazoniurn compound obtained with a coupling component selected from thegroup consisting of a benzene, a naphthalene, a tetrahydroquinoline andphenmorpholine nucleus, wherein said benzene and naphthalene nucleicontain an aliphaticamino group having a I group wherein R: represents amember selected from the group consisting of alkyl, cycloalkyl, allyl,phenyl and iuryl, attached to its aliphatic portion, wherein said.tetrahydroquinoline and phenrnorpholine nuclei contain an aliphaticgroup joined through a carbon atom of the aliphatic group to theirnuclear nitrogen atom and wherein said aliphatic group contains 9.

- -o-( :om

group, wherein R: has the meaning just assigned to it, attached thereto.

While any coupling component of the character above defined can beemployed in the preparation of the azo compounds of our invention, thebenzene and naphthalene coupling components ordinarily employed by uscan be represented by the general formula:

group, wherein R1 and Re have the meaning previously assigned to them,attached to the nuclear nitrogen atom.

Illustrative of the grouping represented by the formula:

may be mentioned -cmcH,o-c -o cm It will be understood that the abovegroups are intended to be illustrative and not limitative of ourinvention. Each oi! these groupings, for example, can be attached to thephenyl, naphthyl, tetrahydroquinoline or phenmorpholine nucleus in themanner previously stated.

The following examples illustrate the preparation of the azo compoundsof our invention:

Example 1 12.6 grams of o-chloroaniline are dissolved in a mixture 01'cc. of water and 25 cc. of 36% hydrochloric. acid. The resultingsolution is cooled to a temperature approximating 0-5 C. by the additionor ice, for example, and diazotized by adding, with stirring, 6.9 partsof sodium nitrite dissolved in water.

21 grams or the ethyl carbonate oi p-hydroxyethyl-m-toluidine having theformula:

are dissolved in a dilute aqueous hydrochloric acid solution and theresulting mixture is cooled to a temperature approximating 0-10 C. Thediazo solution prepared above is then added to this mixture withstirring. After the addition oi. the diazo solution, the mixture ispermitted to stand for a short time following which it is slowly madeneutral to Congo red paper by the addition of sodium acetate. Uponcompletion of the coupling reaction, the dye compound formed isrecovered by filtration, washed with water and dried. The dye compoundobtained colors cellulose acetatesilk a yellow shade.

23.7 grams oi the ethyl carbonate of ethyl- .B-hydroxyethyl aniline canbe substituted for the coupling component of the example to obtain a dyewhich similarly colors cellulose acetate silk a yellow shade. Thediazonium form of 1- amino-2-chloro-4-methylbenzene may also be coupledwith this coupling component. to obtain a dye which colors celluloseacetate silk a yellow shade. Similarly, the diazo form of p-nitroanilinemay also be coupled with both the coupling components mentioned toobtain dyes which color cellulose acetate silk a yellow shade.

Example 2 15 grams of methylanthranilate are diazotized and thediazonium compound obtained is coupled with 31 grams of themethylcarbonate of 'y-hydroxypropylbenzyl-m-toluidine having theformula:

The diazotization and coupling reactions may be carried out as describedin Example 1. The dye compound obtained colors cellulose acetate silk ayellow shade.

Example 3 21.7 grams of 1-amino-2-bromo-4-nitroaniline are diazoti'zedin known fashion and the diazonium compound formed is coupled with 28.3

grams of OCH:

om-oH-om Coupling and recovery of the dye compound may be carried out asdescribed in Example 1. The

. dye compound obtained colors cellulose acetate silk a violet shade.

' Example 4 13.8 grams of p-nitroaniline are diazotized and thediazonium compound obtained is coupled with 31 grams of thedimethylcarbonate of difl-hydroxyethyl-mtoluidine having the formula:

16.3 grams of 1-amino-2-chloro-4-nitrobenzene are diazotized in knownfashion and the diazonium compound obtained is coupled with 26.1 gramsof the methylcarbonate of l-p-hydroxyethylamino-5-naphthol. Coupling andrecovery of the dye compound formed can be carried out in accordancewith the method described in Example 1. The dye compound obtained colorscellulose acetate silk a blue shade.

The coupling component of this example may likewise be coupled with thediazo form of 1'amino-2,4-dinitrobenzene, for example, to obtain a dyewhich colors cellulose acetate silk 9. blue shade. Example 6 26.3 gramsof 1-amino-2,4-dinitro-6-bromobenzene are diazotized in known fashionand the diazonium compound obtained is coupled with 29 grams of themonoethylcarbonate of glyceryl-anaphthylamine. Coupling and recovery of.the

dye compound formed may be carried out in accordance with the methoddescribed in Example 1. The dye compound obtained colors celluloseacetate silk a blue shade.

Example 7 19.7 grams of p-aminoazobenzene are diazotized in knownfashion and the diazonium compound obtained is coupled with 34 grams ofCoupling and recovery of the dye compound formed can be carried out inaccordance with the method described in Example 1. The dye conipoundobtained colors cellulose acetate silk an orange-red shade.

Example 8 13.8 grams of p-nitroaniline are diazotized in known fashionand the diazonium compound obtained is coupled with the ethylcarbonateof- 1-p-hydroxyethylphenmorpholine having the formula: v

Coupling and recovery of the dye compound formed can be carried out inaccordance with the method described-in Example 1. The dye compoundobtained colors cellulose acetate silk a rubine shade.

Example 9 16.3 grams of 1-amino-2-chloro-4-nitrobenzene are diazotizedin known fashion and the diazonium compound obtained is coupled with theethylcarbonate of 1-fi,hydroxyethyltetrahydroquinoline having theformula:

(fHzCHzO-(P-O 02115 Coupling and recovery of the dye compound formed canbe carried out in accordance with the method described in Example 1. Thedye compound obtained colors cellulose acetate silk arubine shade.

- Example 10 13.5 grams of p-aminoacetophenone are diazotized in knownfashion and the diazonium com- 2-methpxy-5-methylbenzene. Coupling andrecovery of the dye compound formed can be car- Example 11 18.3 grams or2,4-dinitroaniline are diazotized in known fashion and the diazoniumcompound obtained is coupled with an equivalent gram ried out inaccordance with the method described 5 v in Example 1. The e comp undolbtained colors g fgg zgg gfi fiz g g fig it acetate silk an P i b0Coupling and recovery of the dye compounds grams the monoe hylcar nateor formed can be carried out in accordance with glycerylbenzylanilme canbe substituted for the the method described in Example 1 The dyecomponent of this example to obtain 10 compounds obtained colorcellulose acetate silk a dye compound which colors cellulose acetatesilk violent shade an orange shade.

Similarly, an equivalent gram molecular weight gzg g g zgfi z fizgg zggz gggz g g: of a 15 vention together with the color they produce on 4 4cellulose acetate silk. The compounds indicated belgw may be upreparedby diazotizing the amines lis d under e heading Amine" and coupling Ethe diazonium compounds obtained with the comv o 0 20 pounds specifiedin the column entitled Coupling component. The dlazotization andcoupling recan be substitu d for h p g component actions may, forexample, be carried out following of the example to obtain a dyecompound which the general procedure described in Examples 1 to colorscellulose acetate silk a red shade. l1, inclusive.

Amine Coupling component Color o-(Cl, Br, F, I)-anillne 1- Mono-methylcarbonate 0! 1-glyoary1amino-3-(C1, Br, F, I)-benzene. Yellowu CaHr Do2. N y Do.

' omcm-o-c-ocflih r I ll) v canon Do 3- N Do.

7 C:HO-CO CHaCHaCHI OCH: 6 0234 8 ON a Do 4- Do.

1 clm-o-c-ocmomomcm H v Do -5. @N-CHz HtCH2CHt-O-E-O 0,11. Do.

' c,m-o-c-o,c1m Do QN\ Do.

OzHr-O-C0 01H;

Do 1. Di-ethyl carbonate oi l-glyoorylsmino-B-mothyl benzene 150. Do s.Qmmm-o-g-o om), Do.

Do 9. N Bic-CHI n0.

1 QaHr-O-C-O-CHa-Jili X111.

/CHz-CH=CH! Do 10. N\ Do.

1 C:H40-C-0C1H; H1 a OCH cyclohexyl Do l1. 'Do.

CSHl-O-COC1HO can HI J Amine Coupling component Color o flmonom-o-ooclfle-ocm H N H =g-NCaHu c Blue N0 NH: )9?

cmonr-o-c -ocm H N Do cmo-N a Do Do 0 H E on.

H: N o tmcnoncm-o-t-omm o1 orncnonr-o-c-oclm N0 Na (an Do. 1 pm Thenuclear sulfonated compounds of our invention can be prepared bysulfonatlon oi the unsulfonated compounds disclosed herein or by the useof previously sulfonated components. Thus, p-nitroaniline-o-sulfonicacid, o-sulfoaniline or 'p-sulfoaniline, for example, can be diazotizedand the diazonium compounds obtained coupled with any of the foregoingcoupling components to obtain dye compounds of our invention which aresuitable for the coloration of wool and silk. The sulfonation operationJust referred to can be carried out in accordance with any suitableknown method.

In order that our invention may be completely understood,'thepreparation of the coupling com-- ponents employed in the preparation ofthe compounds of our invention is given hereinafter. The benzene andnaphthalene coupling components can be prepared by reacting a benzene ornaphthalene compound having a hydroxyaliphaticamino group attached tothe nucleus with a (alky1-, cycloalkyl-, allyl-, phenylor Iuryl-)cholorocarbonate. The phenmorpholine and tetrahydroquinoline couplingcomponents can be prepared by reacting a phenmorpholine ortetrahydroquinoline compound containing a hydroxyaliphatic groupattached to the nuclear nitrogen atom with the chlorocarbonates abovementioned. The reaction can be carried out in the presence of an inertsolvent or diluent medium, such as pyridine, at room temperature. Toillustrate, the methyl carbonate of 'y-hydroxypropyl benzyl-m-toluidinecan be prepared by treating 'y-hydroxypropyl benzyl-m-toluidine withmethylchlorocarbonate; the ethylcarbonate of s-hydroxyethyLm-toluidinecan be prepared by treating c-hydroxyethyl-m-toluidine withethylchlorocarbonate; the iurylcarbonate of ethyl-p hydroxyethylanilinecan be prepared by treating ethyl-p-hydroxyethylaniline withfurylchlorocarbonate; the allyl carbonate of p-hydroxyethylaniline canbeprepared by reacting p-hydroxyethylaniline with allylchlorocarbonateand the cyclohexylcarbonate of 'y-hydroxypropylaniline can be preparedby reacting 'y-hydroxypropylaniline with cyclohexylchlorocarbonate.-

The chlorocarbonate' compounds referred to above can be prepared byreacting the corresponding alcohol with phosgene in the cold.

Thus methylchlorocarbonate, ethylchlorocarbonate, furylchlorocarbonate,cyclohexylchlorocarbonate and allylchlorocarbonate can be prepared byreacting methyl alcohol, ethyl alcohol, turfuryl alcohol, cyclohexylalcohol and allyl alcohol, respectively, with phosgene.

The azo dye compounds of our invention are, for the most part,relatively insoluble in water. Those compounds which are insoluble inwater may be advantageously employed for the direct dyeing of textilematerials by grinding the dye to a fine powder, intimately mixing itwith a suitable dispersing or solubilizing agent, and adding theresulting mixture to water or a dilute solution of soap in water to forman aqueous dyebath. Following this known preparation 0! the dyebath, thetextile materials to be dyed may be added to the dyebath and the dyeingoperation conducted in known fashion. The dye compounds of our inventionwhich are water soluble do not, of course, require the use of adispersing or solubilizing agent but'may be applied to silk, wool and(depending upon the nature and position of the water-solubilizing group)organic derivatives of cellulose textile materials from an aqueoussolution of the dye which may contain salt. For a more completedescription as to how the azo dye compounds of our invention may beemployed in dyeing or coloring operations, reference may be had to ourU. S. Letters Patent No. 2,115,030, issued April 26, 1938. For a moredetailed description as to how the water soluble azo dyes ofour-invention may be employed for the coloration of textile materials,reference may be had to our U. 8. Letters Patent No. 2,107,898, issuedFebruary 8, 1938.

We claim:

1. The azo compounds having formula:

the general A-N'=NR wherein A represents the residue of a memberselected from thegroup-consisting of an aryl nucleus of the benzeneseries anda benzothiazole nucleus, R represents a member selected fromthe group consisting of a phenyl nucleus, a naphthyl nucleus, atetrahydroquinoline nucleus and a phenmorpholine nucleus, wherein saidphenyl and naphthyl nuclei contain an aliphaticamino group in paraposition to the azo bond, said aliphaticamino group having a group,wherein R2 represents a member selected from the group consisting ofalkyl, cycloalkyl, allyl, phenyl and furyl, attached to its aliphaticportion, wherein said tetrahydroquinoline and phenmorpholine nucleicontain an aliphatic group joined through a carbon atom of the aliphaticgroup to their nuclear nitrogen atom and wherein said aliphatic groupcontainsa -C 0Ra group, wherein R2 represents a member selected from thegroup consisting of alkyl, cycloalkyl, allyl, phenyl and furyl, attachedto its aliphatic portion, wherein said tetrahydroquinoline andphenmorpholine nuclei contain an aliphatic group joined through a carbonatom of the aliphatic group to their nuclear nitrogen atom and whereinsaid aliphatic group contains a -o- -o R,

group, wherein R2 has the meaning given above, attached thereto.

3. The azo compounds have the general formula:

' A-N=NR wherein A represents the residue of a member selected from thegroup consisting of an aryl nucleus of tha-benzene series and abenzothiazole nucleus and R represents a phenyl nucleus containing analiphaticamino group in para position to the azo bond, saidaliphaticamino group havmg a O("J--0 R: 0 group, wherein R2 represents amember selected from the group consisting of alkyl, cycloalkyl,

allyl, phenyl and fury].

- 4. Theazo compounds having the general formula:

AN=NR wherein A represents the residue of a member selected from thegroup consisting of an aryl nucleus or the benzene series and abenzothiazole nucleus and R-represents a .tetrahydroquinoline nucleuscontaining an aliphatic group joined through a carbon atomof thealiphatic group to its nuclear nitrogen atom and wherein said aliphaticgroup contains a -o-o-0 a,

group, wherein R2 represents a member selected from the group consistingof alkyl, cycloalkyl, allyl, phenyl and furyl attached thereto.

a 5. The azo compounds having the general formula:

wherein A represents the residue of a member selected from the groupconsisting of an aryl nucleus of the benzene series and a benzothiazolenucleus and R represents a phenmorpholine nucleus containing analiphatic group joined through a carbon atom of the aliphatic group toits nuclear nitrogen atom and wherein I said aliphatic group contains agroup, wherein R2 represents a member selected from the group consistingof alkyl, cycloalkyl, allyl, phenyl and furyl attached thereto.

6. The azo compounds having the general formula:

A-N=NR wherein A represents the residue of an aryl nucleus of thebenzene series, and R represents a phenyl nucleus containing analiphaticamino group in para position, to the azo bond, saidaliphaticamino group having a -0-c-om group, wherein R2 represents amember selected from the group consisting of alkyl, cycloalkyl, allyl,phenyl and furyl attached thereto.

'7. The azo compounds having the general formula:

A--N=NR wherein A represents the residue of a member selected from thegroup consisting of an aryl nucleus of the benzene series and abenzothiazole nucleus, R represents a member selected from the groupconsisting of a phenyl nucleus, a naphthyl nucleus, atetrahydroquinoline nucleus and a phenmo-rpholine nucleus, wherein saidphenyl and naphthyl nuclei contain an aliphaticamino group in paraposition to the azo bond, said aliphaticamino group having a -O-C-Oalkylgroup'attached to its aliphatic portion wherein said tetrahydroquinolineand phenmorpholine nuclei contain an aliphatic group joined to a carbonatom of the aliphatic group to their nuclear nitrogen atom and whereinsaid aliphatic 'group contains a 0(l%0alkyl group attached thereto.

8. The azo compounds having the general formula: V A-N=NR wherein Arepresents the residue of an nucleus of the benzene series, and Rrepresented phenyl nucleus containing an aliphatic amino group in paraposition to the azo bond, said aliphatic amino group having a groupattached to 'its aliphatic portion.

9. Material made of or containing an organic derivative of cellulose iscolored with a nuclear non-sulfonated azo dye compound having thegeneral formula:

whereinA represents the residue of a member selected from the groupconsisting of an aryl nucleus oi the benzene series and a beamthiazolenucleus, R represents a member selectedfrom the group consisting of aphenyl-nucleus, a naphthyl nucleus, a tetrahydroquinoline nucleus and aphenmorpholine nucleus, wherein said phenyl and naphthyl nuclei containan aliphaticamino group'in para position to the azg bond. saidaliphaticamino group having a group, wherein R2 represents a memberselected from the group consisting of alkyl, cycloalkyl, ailyl, phenyland furyl, attached to its aliphatic 1 portion, wherein saidtetrahydroquinoline and phenmorpholine nuclei contain an aliphatic groupjoined through a carbon atom of the aliphatic group to their nuclearnitrogen atom wherein said aliphatic group contains a group, wherein R2has the meaning given above, attached thereto. A

10. Material made of or containing an organic derivative of celluloseand wherein said organic derivative of cellulose is colored with anuclear non-sulionated azo dye compound having the general formula:

wherein A represents the residue of an aryl nucleus oi the benzeneseries, B. represents a memderivative of cellulose and wherein saidorganic 11. Material made of or containing an organic derivative ofcellulose and wherein said organic derivative oi cellulose is coloredwith a nuclear non-sulionated azo dye compound having the,

eneral formula:

A-N=NR wherein A represents the residue 01! an aryl nucleus oi! thebenzene series, and R represents a phenyl nucleus containing analiphaticamino group in para position to the azo bond, saidaliphaticamino group having a group, wherein R2 represents a memberselected from the group consisting of alkyl, cy'cloalkyl, allyl,-phenyland furyl attached thereto.

12. A cellulose acetate colored with a nuclear non sulionated azo dyecompound having the general formula:

' AN=NR I wherein A represents the residue of a member selected from thegroup consisting of an aryl nucleus .0! the benzene series and abenzothia- -zole nucleus, R represents a member selected from the groupconsisting of a phenyl nucleus, a

ber selected from the group consisting of a phenyl nucleus. 2. naphthylnucleus, a tetrahydroquinoline nucleus and phenmorpholine nucleus,wherein said phenyl and naphthyl nuclei contain an aliphaticamino groupin para position to the azo bond, said aliphaticamino group having agroup, wherein R2 represents a member selected from the group consistingof alkyl, cycloalkyl, ally], phenyl and iuryl, attached to its aliphaticportion, wherein said tetrahydroquinoline and phenmorpholine nucleicontain an aliphatic group joined through a carbon atom of the aliphaticgroup to their nuclear nitrogen atom and wherein said aliphatic groupcontains a groupswherein R2 has the meaning given above. attachedthereto.

naphthyl nucleus, a tetrahydroquinoline nucleus and a phenmorpholinenucleus, wherein said phenyl and naphthyl nuclei contain analiphaticamino group in para position to the azo bond, saidaliphaticamino group having a group, wherein R: representsa memberselected from the group consisting of alkyl, cycloalkyl, allyl, phenyland :turyl, attached to its aliphatic portion, wherein saidtetrahydroquinoline and phenmorpholine nuclei contain an aliphatic groupJoined through a carbon atom of the all-- phatic group to their nuclearnitrogen atom and wherein said aliphatic group contains a group, whereinR: has the meaning given above,

' attached thereto.

azo bond, said aliphaticamino group having a group, wherein R2represents a member selected from the group consisting of alkyl,cycloalkyl, ailyl, phenyl and fury], attached to its aliphatic .portion,wherein said tetrahydroquinoline and phenmorpholine nuclei contain analiphatic group Joined through a carbon atom of the aliphatic group totheir nuclear nitrogen atom and wherein said aliphatic group contains a-O (IfORI group, wherein R: has the meaning given above, attachedthereto.

14. A cellulose acetate colored with a nuclear non-sulfonated azo dyecompound having the general formula:

wherein A represents the residue of an aryl nucleus of the benzeneseries, and R represents a phenyl nucleus containing an allphaticaminogroup in para position to the azo bond, said aliphaticamino group havinga -o-( :-0 R2 0 group, wherein R2 represents a member selected from thegroup consisting of alkyl, cycloalkyl, allyl, phenyl and furyl attachedthereto.

aliphatic portion.

- JOSEPH, B. DICKEY.

JAMES G. McNALLY.

group attached to its

